INTRODUCTION

The word ‘thermodynamics’ implies the flow of heat. It deals with energy changes
accompanying all types of physical and chemical processes.

It helps to lay down the criteria for predicting the feasibility or spontaneity of a
process, including a chemical reaction, under a given set of conditions. It also helps
to determine the extent to which a process, including a chemical reaction, can
proceed before the attainment of equilibrium.

Thermodynamics is based on two generalizations called the first and second laws of
thermodynamics. These are based on human experience.

SOME BASIC TERMS

Some Basic Terms

System
A system is defined as any specified portion of matter under study which is
separated from the rest of the universe with a bounding surface. A system may
consist of one or more substances.

Surroundings
The rest of the universe which might be in a position to exchange energy and matter
with the system is called the surroundings.

Types of system
(i) Isolated system

A system which can exchange neither energy nor matter with its surrounding is
called an isolated system.

(ii) Open system

A system which can exchange matter as well as energy with its surroundings is said
to be an open system.

(iii) Closed system

A system which can exchange energy but not matter with its surroundings is called a
closed system.
Macroscopic properties
The properties associated with a macroscopic system (i.e. consisting of large
number of particles) are called macroscopic properties. These properties are
pressure, volume, temperature, composition, density etc.

Extensive and Intensive properties

An extensive property of a system is that which depends upon the amount of the
substance present in the system like mass, volume and energy.

An intensive property of a system is that which is independent of the amount of the

substance present in the system like temperature, pressure, density, concentration,
viscosity, surface tension, refractive index etc.

State of a system
When macroscopic properties of a system have definite values, the system is said to
be in definite state. Whenever there is a change in any one of the macroscopic
properties, the system is said to change into a different state. Thus, the state of a
system is fixed by its macroscopic properties.

State variables
Since the state of a system changed with change in any of the macroscopic
properties, these properties are called state variables or the thermodynamics
parameters which depends only upon the initial and final states of the system and
independent of the manner as to how the change is brought are called state
functions. Some common state functions are internal energy, enthalpy, entropy, free
energy, pressure, temperature, volume etc.

Thermodynamic equilibrium
A system in which the macroscopic properties do not undergo any change with time
is said to be in thermodynamic equilibrium.

Thermodynamic process and their types

The operation by which a system changes form one state to another is called a
process. Whenever a system changes from one state to another it is accompanied
by change in energy. In case of open systems, there may be change of matter as
well.

The following types of process are known

Isothermal process
A process is said to be isothermal if the temperature of the system remains constant
during each stage of the process.

Adiabatic process
A process is said to be adiabatic if the heat enters or leaves the system during any
step of the process.
Isobaric process
A process is said to be isobaric if the pressure of the system remains constant during
each step of the process.

ISOCHORIC PROCESS

ISOCHORIC PROCESS
A process is said to be isochoric if the volume of the system remains constant during
each step of the process.

Reversible and Irreversible process

A process which is carried out infinitesimally slowly in such a manner that the system
remains almost in a state of equilibrium at every stage or a process carried out
infinitesimally slowly so that the driving force is only infinitesimally greater than the
opposing force is called a reversible process.

Any process which does not take place in the above manner i.e. a process which
does not take place infinitesimally slowly, is said to be an irreversible process.

In fact, all the natural processes are irreversible processes.

INTERNAL ENERGY, U/V

Every substance is associated with a definite amount of energy which depends upon
its chemical nature as well as upon its temperature, pressure and volume. This
energy is known as internal energy. Internal energy of the system is the energy
possessed by all its constituent molecules.

Internal energy is a state property i.e. its value depends only upon the state of the
substance but does not depend upon how that state is achieved. The absolute value
of internal energy of a substance can not be determined. However determining the
absolute values of internal energies is neither necessary nor required. It is the
change in internal energy accompanying a chemical or a physical process that is of
interest and this is a measurable quantity.

The first law of thermodynamics

The first law of thermodynamics states that energy can neither be created nor
destroyed, although it can be transformed from one form to another. This is also
known as the law of conservation of energy.

MATHEMATICAL EXPRESSION OF FIRST

LAW

Let UA be the energy of a system in its state A and UB be the energy in its state B.
Suppose the system while undergoing change from state A to state B absorbs heat q
from the surroundings and also performs some work (mechanical or electrical), equal
to w. The absorption of heat by the system tends to raise the energy of the system.
The performance of work by the system, on the other hand, tends to lower the
energy of the system because performance of work requires expenditure of energy.
Hence the change of internal energy, ΔU, accompanying the above process will be
given by

ΔU = UB - UA = q - w

In general, if in a given process the quantity of heat transferred from the surrounding
to the system is q and work done in the process is w, then the change in internal
energy,

ΔU = q + w

This is the mathematical statement of the first law of thermodynamics.

If work is done by the surroundings on the system (as during the compression of a
gas), w is taken as positive so that ΔU = q + w. if however work is done by the
system on the surroundings (as during the expansion of a gas), w is taken as
negative so that ΔU = q – w.

Related Topics

 Hess's Law
 Gibbs Free Energy

ENTHALPY OF A SYSTEM

The quantity U + PV is known as the enthalpy of the system and is denoted by H. It

represents the total energy stored in the system. Thus
H = U + PV

It may be noted that like internal energy, enthalpy is also an extensive property as
well as a state function. The absolute value of enthalpy can not be determined,
however the change in enthalpy can be experimentally determined.

ΔH = ΔU + Δ(PV)

Various kinds of processes:

(i) Isothermal reversible expansion of an Ideal gas: Since internal energy of an Ideal
gas is a function of temperature and it remains constant throughout the process
hence

ΔE = 0 and ΔH = ΔE + ΔPV

∵ΔE = 0

and P1V1 = P2V2 at constant temperature for a given amount of the gas

∴ ΔH= 0

Calculation of q and w:

∵ ΔE = q + w

For an Isothermal process, w = -q

This shows that in an Isothermal expansion, the work done by the gas is equal to
amount of heat absorbed.

and w = - n RT ln(V2/V1) = - n RT ln(P1/P2).

(ii) Adiabatic Reversible Expansion of an Ideal gas:

∵q=0

∴ ΔE= -w.

Total change in the internal energy is equal to external work done by the system.

∴Work done by the system = ΔE= CvΔT.

and Cp-Cv = R

On dividing all the terms by Cv.

and ΔH = ΔE + PΔV.

Thus if T2>T1, w = +ve i.e. work is done on the system.

Thus if T2<T1, w = -ve i.e. work is done by the system.

Limitations of the first law. Need for the second law

A major limitation of the first law of thermodynamics is that its merely indicates that in
any process there is an exact equivalence between the various forms of energies
involved, but it provides no information concerning the spontaneity or feasibility of
the process. For example, the first law does not indicate whether heat can flow from
a cold end to a hot end or not.

The answers to the above questions are provided by the second law of
thermodynamics.

Spontaneous and non – spontaneous process

If in the expansion of a gas the opposing pressure is infinitesimally smaller than the
pressure of the gas, the expansion takes place infinitesimally slowly i.e. reversible. If
however, the opposing pressure is much smaller than the pressure of the gas the
expansion takes place rapidly i.e. irreversibly. Natural processes are spontaneous
and irreversible.
SECOND LAW OF THERMODYNAMICS

The second law of Thermodynamics helps us to determine the direction in which

energy can be transformed. It also helps us to predict whether a given process or
chemical reaction can occur spontaneously or not.

According to Kelvin: “It is impossible to use a cyclic process to extract heat from a
reservoir and to convert it into work without transferring at the same time a certain
amount of heat from a hotter to colder part of the body”.

Entropy Change: Entropy change is the state function and it is the ratio of heat
change in a reversible process by the temperature.

ΔS = qrev/T

Thermodynamically irreversible process is always accompanied by an increase in

the entropy of the system and its surroundings taken together while in a
thermodynamically reversible process, the entropy of the system and its
surroundings taken together remains unaltered.

Physical Significance of Entropy: Entropy is the measure of disorderness because

spontaneous processes are accompanied by increase in entropy as well as increase
in the disorder of the system. Thus, increase in entropy implies increase in disorder.

Some Other State Function: For a spontaneous process entropy change is positive
and if it is zero, the system remains in a state of equilibrium. Two other functions are
also there to decide the feasibility of the reactions like work function A and free
energy change G.

A = E – TS…….(i)

G = H – TS…….(ii)

And ΔA = ΔE - TΔS……(iii)

ΔG = ΔH - TΔS………...(iv) (for a finite change at constant temperature)

Since, ΔS = qrev./T Hence from eq. (i)

∴ΔA = ΔE – qrev………………..(v)

and according to first law of Thermodynamics

ΔE - qrev = wrev. …………….(vi)

If during the change, work is done by the system, it would carry a negative sign,
-wrev = ΔE – qrev…………….(vii)

Comparing the equation (v) and (vii)

-ΔA = wrev

Since the process is carried out reversibly w represents the maximum work. It is thus
clear that decrease in function A gives maximum work done that can be done by the
system during the given change. The work function A is also called as Helmholtz
function.

From equation (iv)

ΔG = ΔH - TΔS

and ΔH = ΔE + PΔV

∴ΔG = ΔE + PΔV - TΔS

Comparing it with eq. (iii)

ΔG = ΔA + PΔV

Since, ΔA is equal to – w, hence.

ΔG = - w + PΔV.

- ΔG = w- PΔV

Hence decrease in free energy gives maximum work obtainable from a system other
than that due to change of volume at constant temperature and pressure. This is
called as Net Work.

Net Work = w-PΔV = -ΔG

The Net Work may be electrical work or chemical work.

Criterion of spontaneity: For a spontaneous process ΔG should be -ve

GIBBS FREE ENERGY

This is another thermodynamic quantity that helps in predicting the spontaneity of a

process, is called Gibbs energy (G).

It is defined mathematically by the equation.

G = H − TS
Where H = heat content

S = entropy of the system

T = absolute temperature

Free energy change

For isothermal process.

ΔG = G2 -G1 = ΔH - TΔS

ΔG = change in Gibbs free energy of the system.

It is that thermodynamic quantity of a system the decrease in whose value during a

process is equal to the maximum possible useful work that can be obtained from the
system.

RELATIONSHIP BETWEEN FREE ENERGY

AND EQUILIBRIUM CONSTANT

The free energy change of the reaction in any state, ΔG (when equilibrium has not
been attained) is related to the standard free energy change of the reaction, ΔG0
(which is equal to the difference in free energies of formation of the products and
reactants both in their standard states) according to the equation.

ΔG = ΔG0 + RTINQ

Where Q is the reaction quotient

When equilibrium is attained, there is no further free energy change i.e. ΔG = 0 and
Q becomes equal to equilibrium constant. Hence the above equation becomes.

ΔG0 = -RTInK(eq.)

or ΔG0 = - 2.303RT logK(eq.)

In case of galvanic cells. Gibbs energy change ΔG is related to the electrical work
done by the cell.

ΔG = −nFE(cell) where n = no. of moles of electrons involved

F = the Faraday constant

E = emf of the cell

If reactants and products are in their standard states ΔG0 = -nFE0cell

THIRD LAW OF THERMODYNAMICS

The third law of thermodynamics states that the entropy of a perfect crystal is zero at
a zero Kelvin temperature. (Zero Kelvin temperature is also called absolute zero).

Explanation:
As the temperature of any system decreases, the atom and molecules in the system
lose their energy and approach their lowest energy points, by doing so atom &
molecule’s kinetic energy decreases and hence their random motion.

Since Entropy is the measurement of the randomness of any closed system. So,
when absolute zero temperature is achieved, the atom and molecules of the crystal
have the lowest energy and hence no randomness in the particles. So, zero entropy
of the system was observed.

Mathematical Application:
Let for any solid S00 is entropy at zero kelvin and S is entropy at T kelvin.

So, ∆S = S – S0

Also, we know

Since S0 = 0 at by third law.

So,

By this we can calculate the absolute entropy of any solid at temperature T.

THERMOCHEMISTRY

The branch of chemistry which deals with energy changes involved in chemical
reactions is called thermochemistry. The energy change that occurs in a chemical
reactions is largely due to change of bond energy.

Change of internal energy in a chemical reaction

Let us consider a chemical reaction taking place at constant temperature and at
constant volume. In such a case, w = 0 and hence from the first law
ΔU = qv

Where qv is the heat exchanged at constant volume, or heat or enthalpy of reaction

at constant volume.

Change of Enthalpy in a chemical reaction

Let qP be the heat exchanged in the chemical reaction taking place at constant
pressure, Then evidently,

ΔH = qP = Heat or Enthalpy of reaction at constant pressure.

Exothermic and Endothermic reaction

Reaction that give out heat, i.e. which are accompanied by evolution of heat, are
called exothermic reaction. In such reactions ΔH is negative. On the other hand,
reaction that intake heat, i.e. which are accompanied by absorption of heat are called
endothermic reactions. In these reactions ΔH is positive.

Enthalpy of reaction
It is the enthalpy change taking place during the reaction when the number of moles
of reactants and products are same as the stoichiometric coefficient indicates in the
balanced chemical equation. The enthalpy change of the reaction depends upon the
conditions like temperature, pressure etc under which the chemical reaction is
carried out. Therefore, it is necessary to select the standard state conditions.
According to thermodynamics conventions, the standard state refers to 1 bar
pressure and 298 K temperature. The enthalpy change of a reaction at this standard
state conditions is called standard enthalpy of the reaction (ΔH°)

Different types of enthalpy

(i) Enthalpy of formation: Enthalpy change when one mole of a given compound is
formed from its elements.

H2(g) + 1/2O2(g) → 2H2O(l), ΔH = –890.36 kJ / mol

(ii) Enthalpy of combustion: Enthalpy change when one mole of a substance is burnt
in oxygen.

CH4 + 2O2(g) → CO2 + 2H2O(l), ΔH = –890.36 kJ / mol

(iii) Enthalpy of Neutralization: Enthalpy change when one equivalent of an acid is

neutralized by a base or vice – versa in dilute solution. This is constant and its value
is –13.7 kcal for neutralization of any strong acid by a base since in dilute solutions
they completely dissociate into ions.

H+ (aq) + OH– (aq) → H2O(l), ΔH = –13.7 kcal

For weak acids and bases, heat of neutralization is different because they are not
dissociated completely and during dissociation some heat is absorbed. So total heat
evolved during neutralization will be less.

e.g. HCN + NaOH → NaCN + H2O, ΔH = –2.9 kcal

Heat of ionization in this reaction is equal to (–2.9 + 13.7) kcal = 10.8 kcal

(iv) Enthalpy of hydration: Enthalpy of hydration of a given anhydrous or partially

hydrated salt is the enthalpy change when it combines with the requisite no.of mole
of water to form a specific hydrate. For example, the hydration of anhydrous copper
sulphate is represented by

CuSO4(s) + 5H2O (l) → CuSO45H2O(s), ΔH° = –18.69 kcal

(v) Enthalpy of Transition: Enthalpy change when one mole of a substance is
transformed from one allotropic form to another allotropic form.

C (graphite) → C(diamond), ΔH° = 1.9 kJ/mol

HESS'S LAW

This law states that the amount of heat evolved or absorbed in a process, including a
chemical change is the same whether the process takes place in one or several
steps.

Suppose in a process the system changes from state A to state B in one step and
the heat exchanged in this change is q. Now suppose the system changes from state
A to state B in three steps involving a change from A to C, C to D and finally from D
to B. If q1, q2 and q3 are the heats exchanged in the first, second and third step,
respectively then according to Hess’s law

q 1 + q2 + q3 = q

Hess’s law is simply a corollary of the first law of thermodynamics. It implies that
enthalpy change of a reaction depends on the initial and final state and is
independent of the manner by which the change is brought about.

APPLICATION OF HESS’S LAW

1. Calculation of enthalpies of formation

There are large number of compounds such as C6H6, CO, C2H6 etc whose direct
synthesis from their constituent element is not possible. Their ΔH0f values can be
determined indirectly by Hess’s law. e.g. let us consider Hess’s law cycle for CO2 (g)
to calculate the ΔH0f of CO(g) which can not determined otherwise.
According to Hess’s law,

= −393 − (−283) ⇒ −110 KJ/mole

2. Calculation of standard Enthalpies of reactions

From the knowledge of the standard enthalpies of formation of reactants and
products the standard enthalpy of reaction can be calculated using Hess’s law.

According to Hess’s law

3. In the calculation of bond energies

BOND ENERGY
Bond energy for any particular type of bond in a compound may be defined as the
average amount of energy required to dissociate one mole, viz Avogadro’s number
of bonds of that type present in the compound. Bond energy is also called the
enthalpy of formation of the bond.

Calculation:
For diatomic molecules like H2, O2, N2, HCl, HF etc, the bond energies are equal to
their dissociation energies. For polyatomic molecules, the bond energy of a particular
bond is found from the values of the enthalpies of formation. Similarly the bond
energies of heteronuclear diatomic molecules like HCl, HF etc can be obtained
directly from experiments or may be calculated from the bond energies of
homonuclear diatomic molecules.
LATTICE ENERGY OF AN IONIC CRYSTAL
(BORN–HABER CYCLE)

The change in enthalpy that occurs when 1 mole of a solid crystalline substance is
formed from its gaseous ions, is known as Lattice energy.

Step 1: Conversion of metal to gaseous atoms

M(s) → M(g) , ΔH1 = sublimation

Step 2: Dissociation of X2 molecules to X atoms

X2(g) → 2X (g), ΔH2 = Dissociation energy

Step 3: Conversion of gaseous metal atom to metal ions by losing electron

M(g) → M+ (g) + e–, ΔH3 = (Ionization energy)

Step 4: X(g) atoms gain an electron to form X– ions

X(g) + e– → X–(g), ΔH4 = Electron affinity

Step 5: M+ (g) and X– (g) get together and form the crystal lattice

M+ (g) + X– (g) → MX(s) ΔH5 = lattice energy

Applying Hess’s law we get

ΔH1 + 1/2 ΔH2 + ΔH3 + ΔH4 + ΔH5 = ΔHf (MX)

On putting the various known values, we can calculate the lattice energy.

BOMB CALORIMETER
The bomb calorimeter used for determining change in internal energy at constant
volume if reaction for the combustion is known than enthalpy of combustion can be
estimated by using formula
ΔH = ΔE + ΔnRT.

This apparatus was devised by Berthelot (1881) to measure the heat of combustion
of organic compounds. A modified form of the apparatus shown in Figure consists of
a sealed combustion chamber, called a bomb, containing a weighed quantity of the
substance in a dish along with oxygen under about 20 atm pressure. The bomb is
lowered in water contained in an insulated copper vessel. This vessel is provided
with a stirrer and a thermometer reading up to 1/100th of a degree. It is also
surrounded by an outer jacket to ensure complete insulation from the atmosphere.
The temperature of water is noted before the substance is ignited by an electric
current. After combustion, the rise in temperature of the system is noted on the
thermometer and heat of combustion can be calculated from the heat gained by
water and the calorimeter. By knowing the heat capacity of calorimeter and also the
rise in temperature, the heat of combustion can be calculated by using the
expression

Heat exchange = Z × ΔT

Z–Heat capacity of calorimeter system

ΔT– rise in temp

Heat changes at constant volumes are expressed in ΔE and Heat changes at

constant pressure are expressed in ΔH. Also, ΔH = ΔE + ΔnRT

Δn = gaseous product moles – gaseous reactant moles.

Application of bond energies

(i) Determination of enthalpies of reactions

Suppose we want to determine the enthalpy of the reaction.

If bond energies given for C ⎯ C, C = C, C⎯H, and H ⎯ H are 347.3, 615.0, 416.2 and
435.1KJ mol−1 respectively.
= (615.0 + 435.1) − (347.3 + 832.4) ⇒ −129.6 KJ

(ii) Determination of enthalpies of formation of compounds

Consider the formation of acetone.

by putting the value of different bond energies you can determine the ΔHf.

(iii) Determination of resonance energy

If a compound exhibits resonance, there is a considerable difference between the
enthalpies of formation as calculated from bond energies and those determined
experimentally. As an example we may consider the dissociation of benzene.

Assuming that benzene ring consists of three single and three double bonds
(Kekule’s structure) the calculated dissociation energy comes out to be 5384.1 KJ
from bond energies data.

The experimental value is known to be 5535.1 KJ/mol. Evidently, the energy required
for the dissociation of benzene is 151 KJ more that the calculated value. The
difference of 151 KJ gives the resonance energy of benzene.

HEAT CAPACITY AND SPECIFIC HEAT

The heat capacity (C) of a sample of a substance is the quantity of heat needed to
raise the temperature of the sample of substance one degree Celsius (or Kelvin).

q = cΔt

Heat capacity is directly proportional to the amount of substance.

The specific heat capacity is the quantity of heat required to raise the temperature of
one gram of a substance by one degree Celsius at constant pressure.

q = s ×m × Δt

where q is the heat required to raise temperature

m = mass in grams

s = specific heat of the substance

Δt = temperature difference

VARIATION OF HEAT OF REACTION WITH

TEMPERATURE
The heat of reaction depends on the temperature. The relation between the two is
known as Kirchoff’s equation.

1. = ΔCP

2. = ΔCV

ΔCP = molar heat capacity of products – molar heat capacity of reactants (at
constant pressure)

ΔCv = molar heat capacity of products – molar heat capacity of reactants (at
constant volume)